Polyol pre-mixes having improved shelf life

ABSTRACT

A polyol pre-mix containing at least one halogenated hydroolefin blowing agent and having improved shelf life stability is provided, wherein each polyol combined with the halogenated hydroolefin blowing agent has an apparent pH of between 3 and 11.4. Controlling the apparent pH of the polyol(s) enables the polyol pre-mix to be stored for extended periods of time and then used in combination with organic polyisocyanate to produce foam formulations having gel times and tack free times not significantly different from those exhibited when freshly prepared polyol pre-mix is used.

The present application claims priority to U.S. Provisional PatentApplication Ser. No. 62/220,329 filed Sep. 18, 2015.

FIELD OF THE INVENTION

The present invention relates to a method of improving the shelf life ofpolyol pre-mixes that contain halogenated hydroolefin blowing agents,including hydrochlorofluoroolefin blowing agents such as HCFO-1233zd.

BACKGROUND OF THE INVENTION

The Montreal Protocol for the protection of the ozone layer mandated thephase out of the use of chlorofluorocarbons (CFCs). Materials more“friendly” to the ozone layer, such as hydrofluorocarbons (HFCs), e.g.,HFC-134a, replaced chlorofluorocarbons. The latter compounds have provento be greenhouse gases, causing global warming and are subject toreduction that is coordinated by the United Nations Framework Conventionon Climate Change (UNFCCC). The emerging replacement materials,hydrofluoropropenes, were shown to be environmentally acceptable as theyhave zero ozone depletion potential (ODP) and acceptable low globalwarming potential (GWP).

Currently used blowing agents for thermoset foams include HFC-134a,HFC-245fa, HFC-365mfc (that have relatively high global warmingpotential) and hydrocarbons such as pentane isomers (that are flammableand have low energy efficiency). Therefore, new alternative blowingagents are being sought. Halogenated hydroolefinic materials such ashydrofluoropropenes and/or hydrochlorofluoropropenes have generatedinterest as replacements for HFCs. The inherent chemical instability ofthese materials in the lower atmosphere provides for a low globalwarming potential and zero or near zero ozone depletion propertiesdesired.

However, the preparation of satisfactory thermoset foams using suchhalogenated hydroolefinic materials as blowing agents can bechallenging, due to certain shelf-life issues. In commercial practice,blowing agents typically are combined with polyols and possibly othercomponents such as surfactant and catalyst to form so-called “B-side”pre-mixes that are then stored for several days to several months priorto being combined with an “A-side” component containing a reactant suchas isocyanate that is capable of reacting with the polyol to form athermoset foam. Ideally, the characteristics of the thermoset foamthereby obtained should not be significantly affected by the length oftime the polyol pre-mix has aged prior to such use. However, asdisclosed by US 2009/0099272 A1, “A shortcoming of two-componentsystems, especially those using certain hydrohaloolefins, including,HFO-1234ze and HFCO-1233zd is the shelf-life of the B-side composition.Normally when a foam is produced by bringing together the A and Bcomponent, a good foam is obtained. However, if the polyol premixcomposition is aged, prior to treatment with the polyisocyanate, thefoam are of lower quality and may even collapse during the formation offoam.”

SUMMARY OF THE INVENTION

It was unexpectedly discovered that selecting and controlling theapparent pH of polyols present in a halogenated hydroolefin blowingagent-containing pre-mix to be stored for some period of time, prior tobeing combined with an isocyanate or other reactant to form a thermosetfoam, improves the shelf life of the pre-mix.

A first embodiment of the invention provides a polyol pre-mixcomprising:

-   -   a) at least one blowing agent, including at least one        halogenated hydroolefin blowing agent; and    -   b) a polyol component comprised of at least one polyol;    -   wherein each polyol of the polyol component has an apparent pH        of at least 3 but no greater than 11.4.

In a second embodiment, each polyol of the polyol component has anapparent pH of at least 4 but no greater than 11.

In a third embodiment, each polyol of the polyol component has anapparent pH of at least 4 but no greater than 10.

In a fourth embodiment, each polyol of the polyol component has anapparent pH of at least 4 but no greater than 9.

In a fifth embodiment, the polyol component in any of the first throughfourth embodiments is comprised of one more polyols selected from thegroup consisting of polyether polyols, polyester polyols,polyether/ester polyols and combinations thereof.

In a sixth embodiment, the polyol component in any of the first throughfifth embodiments is comprised of one or more polyols havingfunctionalities of from 2 to 7.

In a seventh embodiment, the polyol component in any of the firstthrough sixth embodiments is comprised of at least one polyether polyoland at least one polyester polyol.

In an eighth embodiment, the polyol component in any of the firstthrough sixth embodiments contains 0 to 100 parts by weight polyesterpolyol per 100 parts by weight total polyol component and 100 to 0 partsby weight polyether polyol per 100 parts by weight total polyolcomponent.

In a ninth embodiment, the polyol component in any of the first throughseventh embodiments contains 10 to 90 parts by weight polyester polyolper 100 parts by weight total polyol component and 90 to 10 parts byweight polyether polyol per 100 parts by weight total polyol component.

In a tenth embodiment, the polyol component in any of the first throughseventh embodiments contains 20 to 80 parts by weight polyester polyolper 100 parts by weight total polyol component and 80 to 20 parts byweight polyether polyol per 100 parts by weight total polyol component.

In an eleventh embodiment, the polyol component in any of the firstthrough seventh or ninth or tenth embodiments is comprised of at leastone polyether polyol and at least one aromatic polyester polyol.

In a twelfth embodiment, each polyol of the polyol component in any ofthe first through eleventh embodiments has a viscosity of from 400 to60,000 cps at 25° C.

In a thirteenth embodiment, each polyol of the polyol component in anyof the first through twelfth embodiments has a number average molecularweight of from 250 to 6500 Daltons.

In a fourteenth embodiment, the at least one halogenated hydroolefinblowing agent in the polyol pre-mix of any of the first throughthirteenth embodiments is selected from the group consisting ofhydrofluoroolefins, hydrochlorofluoroolefins, and combinations thereof.

In a fifteenth embodiment, the at least one halogenated hydroolefinblowing agent in the polyol pre-mix of any of the first throughfourteenth embodiments includes HFCO-1233zd.

In a sixteenth embodiment, the polyol pre-mix of any of the firstthrough fifteenth embodiments is additionally comprised of at least onesurfactant.

In a seventeenth embodiment, the polyol pre-mix of any of the firstthrough sixteenth embodiments is additionally comprised of at least onecatalyst.

In an eighteenth embodiment, the polyol pre-mix of any one of the firstthrough fifteenth embodiments is additionally comprised of at least onesurfactant and at least one catalyst.

In a nineteenth embodiment, a polyurethane or polyisocyanurate foam isprovided which is the reaction product of a polyol pre-mix in accordancewith any one of the first through eighteenth embodiments and at leastone organic polyisocyanate.

In a twentieth embodiment, a method of making a polyurethane orpolyisocyanurate foam is provided which comprises reacting a polyolpre-mix in accordance with any one of the first through eighteenthembodiments and at least one organic polyisocyanate.

In a twenty-first embodiment, the method of the twentieth embodiment iscarried out such that the polyol pre-mix is prepared by blending the atleast one blowing agent and the polyol component and aging the resultingpolyol pre-mix for at least one month at ambient temperature prior toreacting the polyol pre-mix with the at least one organicpolyisocyanate.

In a twenty-second embodiment, a method of making a polyol pre-mixhaving improved shelf life is provided, wherein the method comprisesselecting a polyol or plurality of polyols, measuring the apparent pH ofeach polyol, confirming that the measured apparent pH of each polyol iswithin the range of 3 to 11.4, and combining the polyol or plurality ofpolyols with at least one blowing agent, including at least onehalogenated hydroolefin blowing agent, to form the polyol pre-mix.

In a twenty-third embodiment, the method of the twenty-second embodimentcomprises an additional step of adjusting the apparent pH of at leastone polyol prior to combining the polyol or plurality of polyols withthe at least one halogenated hydroolefin blowing agent.

In a twenty-fourth embodiment, the method of the twenty-third embodimentis performed such that the adjusting of the apparent pH is carried outby combining the polyol with at least one H⁺ containing compound such asan organic acid, inorganic acid, or combination of organic acid andinorganic acid.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to polyol pre-mixes which have improvedshelf life. That is, the pre-mixes, which contain polyol and halogenatedhydroolefin blowing agent, are capable of being stored at ambientconditions for extended periods of time without significant changes intheir performance when used to prepare thermoset foams.

The blowing agent in the pre-mixes of the present invention comprisesone or more halogenated hydroolefins such as hydrofluoroolefins (HFOs)and/or hydrochlorofluoroolefins (HCFOs), optionally in combination withone or more other types of blowing agents such as hydrofluorocarbons(HFCs), hydrofluoroethers (HFEs), hydrocarbons, alcohols, aldehydes,ketones, ethers/diethers or carbon dioxide.

Thus, in one embodiment, the blowing agent in the pre-mix of the presentinvention is a hydrofluoroolefin or a hydrochlorofluoroolefin, alone orin a combination. Preferred hydrofluoroolefin (HFO) blowing agentscontain 3, 4, 5, or 6 carbons, and include but are not limited topentafluoropropenes; tetrafluoropropenes such as1,3,3,3-tetrafluoropropene (HFO 1234ze, E and Z isomers),2,3,3,3-tetrafluoropropene (HFO 1234yf), 1,2,3,3-tetrafluoropropene(HFO1234ye); trifluoropropenes such as 3,3,3-trifluoropropene (1243zf);tetrafluorobutenes such as HFO 1345; pentafluorobutene isomers such asHFO1354; hexafluorobutene isomers such as HFO1336 (e.g. z-1336mzz);heptafluorobutene isomers such as HFO1327; heptafluoropentene isomerssuch as HFO1447; octafluoropentene isomers such as HFO1438;nonafluoropentene isomers such as HFO1429; HCFOs such as1-chloro-3,3,3-trifluoropropene (HCFO-1233zd),2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), HCFO 1223,1,2-dichloro-1,2-difluoroethene (E and Z isomers),3,3-dichloro-3-fluoropropene, 2-chloro-1,1,1,4,4,4-hexafluorobutene-2 (Eand Z isomers), 2-chloro-1,1,1,3,4,4,4-heptafluorobutene-2 (E and Zisomers). Particularly advantageous blowing agents in the pre-mixes ofthe present invention comprise unsaturated halogenated hydroolefins withnormal boiling points less than about 60° C.

In one embodiment, the blowing agent comprises, consists essentially of,or consists of 1-chloro-3,3,3-trifluoropropene, E and/or Z HCFO-1233zd.A major or predominant portion of the HCFO-1233zd may be the transisomer. For example, in various embodiments the weight ratio of transand cis isomers of HFCO-1233zd present in the blowing agent used is100:0 to 70:30; 100:0 to 90:10; or 100:0 to 97:3.

The halogenated hydroolefin blowing agents in the pre-mix of the presentinvention can be used alone or in combination with other blowing agentsincluding but not limited to: (a) hydrofluorocarbons including but notlimited to difluoromethane (HFC-32); 1,1,1,2,2-pentafluoroethane(HFC-125); 1,1,1-trifluoroethane (HFC143a); 1,1,2,2-tetrafluorothane(HFC-134); 1,1,1,2-tetrafluoroethane (HFC-134a); 1,1-difluoroethane(HFC-152a); 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea);1,1,1,3,3-pentafluopropane (HFC-245fa); 1,1,1,3,3-pentafluobutane(HFC-365mfc) and 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC-4310mee);(b) hydrocarbons including but not limited to, pentane isomers(iso-pentane, n-pentane, cyclo-pentane) and butane isomers; (c)hydrofluoroethers (HFE) such as, C₄F₉OCH₃ (HFE-7100), C₄F₉OC₂H₅(HFE-7200), CF₃CF₂OCH₃ (HFE-245cb2), CF₃CH₂CHF₂ (HFE-245fa), CF₃CH₂OCF₃(HFE-236fa), C₃F₇OCH₃ (HFE-7000),2-trifluoromethyl-3-ethoxydodecofluorohexane (HFE-7500),1,1,1,2,3-hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)-pentane(HFE-7600),1,1,1,2,2,3,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)pentane(HFE-7300), ethyl nonafluoroisobutyl ether/ethyl nonafluorobutyl ether(HFE-8200), CHF₂OCHF₂, CHF₂OCH₂F, CH₂FOCH₂F, CH₂FOCH₃, cyclo-CF₂CH₂CF₂O,cyclo-CF₂CF₂CH₂O, CHF₂CF₂CHF₂, CF₃CF₂OCH₂F, CHF₂OCHFCF₃, CHF₂OCF₂CHF₂,CH₂FOCF₂CHF₂, CF₃OCF₂CH₃, CHF₂CHFOCHF₂, CF₃OCHFCH₂F, CF₃CHFOCH₂F,CF₃OCH₂CHF₂, CHF₂OCH₂CF₃, CH₂FCF₂OCH₂F, CHF₂OCF₂CH₃, CHF₂CF₂OCH₃ (HFE254pc), CH₂FOCHFCH₂F, CHF₂CHFOCH₂F, CF₃OCHFCH₃, CF₃CHFOCH₃, CHF₂OCH₂CHF₂,CF₃OCH₂CH₂F, CF₃CH₂OCH₂F, CF₂HCF₂CF₂OCH₃, CF₃CHFCF₂OCH₃, CHF₂CF₂CF₂OCH₃,CHF₂CF₂CH₂OCHF₂, CF₃CF₂CH₂OCH₃, CHF₂CF₂OCH₂CH₃, (CF₃)₂CFOCH₃,(CF₃)₂CHOCHF₂, (CF₃)₂CHOCH₃, and mixture thereof; (d) C1 to C5 alcohols,C1 to C4 aldehydes, C1 to C4 ketones, C1 to C4 ethers and diethers, C1to C6 hydrocarbons, e.g. iso-, normal, cyclo-pentane; (e) water, (f)carbon dioxide; (g) trans-1,2-dichloroethylene; and (h) methylformate,methylacetate, ethyl formate, and dimethoxymethane.

It has been found that the shelf stability of a pre-mix containinghalogenated hydroolefin blowing agent may be significantly affected bythe apparent pH of the polyol or polyols comprising the polyol componentof the pre-mix. In particular, undesirably large increases in gel timeand/or tack free time may be exhibited by a polyol pre-mix after beingstored for a period of time, if the apparent pH of the polyol(s) is notcontrolled. For consistency and reproducibility in a foam manufacturingoperation, it will be advantageous if the gel time and/or tack free timeexhibited by a polyol pre-mix when combined with an organicpolyisocyanate or other hydroxyl-reactive component to form a foamincrease less than 40%, less than 25%, less than 15% or even less than10% after the polyol pre-mix has been stored for six months at ambienttemperature (e.g., 23° C.). As used herein, “gel time” means the timefrom the beginning of mixing to the point at which the first stringforms using a standard tongue depressor to pull upward or resistance offoam forming is felt from under the foam surface. Typically, it will bedesirable for the gel time of such systems to be relatively brief, e.g.,1 to 300 seconds. As used herein, “tack free time” means the time fromthe beginning of mixing to the point that the outer skin of the foamloses its stickiness.

As used herein, the term “apparent pH” means the pH of a polyol asmeasured in accordance with the following test method:

Reagents

-   -   Isopropanol-water (10/6 v/v)-mix 10 parts of IPA (ACS Reagent        grade, fresh bottle) and    -   6 parts of distilled water    -   Hydrochloric acid, ˜0.001N, aqueous    -   Sodium hydroxide, ˜0.001N, aqueous    -   Buffer solutions, pH 7.0 and 4.0

Apparatus

-   -   Expanded scale pH meter or equivalent    -   Glass electrode, Corning #476022 or equivalent    -   Calomel electrode, sleeve-type, Corning #476162 or equivalent    -   Beaker, 100-mL graduated    -   Magnetic stirrer with stirring bar    -   Autodispenser, 50-mL

Procedure

-   -   1. Calibrate the pH meter with pH 4.0 and 7.0 buffers using the        procedure recommended by the instrument manufacturer.    -   2. Dispense 50 mL of IPA-water into a 100-mL beaker.    -   3. Immerse the tips of the electrodes into the solvent to a        depth not to exceed one-quarter inch above the sleeve of the        reference electrode.    -   4. Add a stirring bar and stir at ˜200 rpm.    -   5. Adjust the pH of the solvent to 7.00±0.01 with dilute sodium        hydroxide or dilute hydrochloric acid added dropwise. Only        adjust one way. Do not back adjust.    -   6. Remove electrodes and weigh 10.0±0.1 g sample into the        neutralized solvent.    -   7. Stir until the sample is dissolved.    -   8. Immerse the tips of the electrodes into the solution as in        step 3. Adjust stirring as in step 4.    -   9. Allow meter to stabilize. This may take several minutes.    -   10. Read the pH to the nearest 0.01 pH unit.

This test method is also described in Carey et al., Apparent pH ofPolyether Polyols—A Comparison of Methods, Polyurethanes 90, Proceedingsof the SPI 33^(rd) Annual Technical/Marketing Conference, pp. 289-296(under the section heading “Standard IPA-Water Method”).

To improve the shelf stability of a pre-mix containing at least onehalogenated olefin blowing agent, each polyol present in the pre-mixshould have an apparent pH of at least 3 but no greater than 11.4. Inone embodiment, each polyol of the polyol component has an apparent pHof at least 4. In other embodiments, each polyol of the polyol componenthas an apparent pH no greater than 11, no greater than 10, or no greaterthan 9.

In embodiments of the invention in which the polyol pre-mix containsmore than one polyol, the apparent pH of the blended polyols isadvantageously at least 3 but no greater than 11.4. The blend of polyolsin the pre-mix may, for example, have an apparent pH of at least 4and/or an apparent pH no greater than 11, no greater than 10 or nogreater than 9.

Although, generally speaking, any type of polyol or combination ofdifferent types of polyols may be utilized in the pre-mixes of thepresent invention (provided the apparent pH limitations set forth hereinare met), in various embodiments of the invention the polyol or polyolsis or are selected from the group consisting of polyether polyols,polyester polyols, polyether/ester polyols and combinations thereof.

The processes used to make each polyol may be varied or selected so asto directly provide polyol having the desired apparent pHcharacteristics. For example, the catalyst(s), initiator(s), and/orreactant(s)/monomer(s) employed and also the conditions under which apolyol is prepared and purified may be chosen so that the resultingpolyol has an apparent pH within certain parameters, in accordance withthe various embodiments of the invention. For example, if a highly basiccatalyst is utilized to prepare a polyol, the polyol product may betreated with an adsorbent or neutralizing agent so as to remove orneutralize the residual basic catalyst, thereby lowering the apparent pHof the polyol. Alternatively or additionally, the apparent pH of analready-prepared polyol may be adjusted through the addition of anappropriate quantity of acid and/or base.

Polyether polyols are well known in the art and may, for example, beprepared by reacting an active hydrogen-containing initiator compound(or mixture of such compounds) with one or more alkylene oxides such asethylene oxide and/or propylene oxide. Typically, base catalysis isemployed for such purpose, with the base subsequently being removed orneutralized prior to use of the polyether polyol. Suitable initiatorcompounds can contain two or more active hydrogens per molecule, such asmay be provided by hydroxyl (—OH) groups or primary or secondary amino(—NH₂ or —NHR) groups. The alkylene oxide(s) react with the initiatorcompound so as to add oxyalkylene groups onto the hydroxyl or aminogroups, with additional alkylene oxide then reacting with thealkoxylated initiator compound to form polyether chains originating fromwhat originally had been the position of the active hydrogen-containingfunctional group(s). Suitable initiator compounds may, in variousembodiments of the invention, contain two to eight, two to seven or twoto six active hydrogens per molecule, which will generally yieldpolyether polyols having functionalities corresponding approximately tothe number of active hydrogens in the initiator compound. As usedherein, the term “functionality” (e.g., as used to refer to a polyetherpolyol having a functionality of 3) means the average number ofisocyanate-reactive functional groups (e.g., hydroxyl groups) permolecule. In certain embodiments of the invention, the polyol componentis comprised of at least one polyol having a functionality greater than2 or at least one polyol having a functionality of 3 or more. Examplesof suitable initiator compounds include, but are not limited to,glycerin, trimethylolpropane, aminoalcohols such as ethanolamine,diethanolamine and triethanolamine, pentaerythritol, dipentaerythritol,α-methyl glucoside, xylitol, sugars (such as sucrose), sugar alcohols(such as sorbitol), mono- and oligomeric glycols such as ethyleneglycol, propylene glycol, diethylene glycol, dipropylene glycol and thelike, polyamines (such as ethylene diamine, toluene diamine, diethylenetriamine, diaminodiphenylmethane and polymethylene polyphenylenediamine), aromatic amines, Mannich bases, Novolacs (phenol-formaldehyderesins), and combinations thereof (such as a mixture of sucrose andglycerin or a mixture of sorbitol and glycerin).

Ethylene oxide can be used in conjunction with propylene oxide toproduce a variety of copolymer polyol structures: as an end-cap (ortip), or as a block in the polymer chain, or as a “random copolymer”formed by polymerizing ethylene oxide and propylene oxide together, aswell as a combination of two or more of these types of structures. Incertain embodiments of the invention, polyether polyols may be usedwhich are ethylene oxide homopolymers, propylene oxide homopolymers, orethylene oxide/propylene oxide copolymers (e.g., block, gradient,random, or other types of copolymers) wherein the weight ratio of EO:POmay be from 1:99 to 99:1.

For example, in various embodiments of the invention, a polyether polyolis used which is a propylene oxide/ethylene oxide copolymer containingtwo or more hydroxyl-terminated polyether chains extending from aresidue of an initiator compound, wherein the polyether chains eachcontain an inner block and an outer block, wherein the inner block ofeach of said polyether chains has a molecular weight of from about 150to 350 and contains from 10 to 35% by weight of oxypropylene units andfrom 65 to 90% by weight of oxyethylene units, and the outer block ofeach of said polyether chains contains from 95 to 100% by weightoxypropylene units and from 0 to 5% by weight oxyethylene units, andfurther wherein the propylene oxide/ethylene oxide copolymer has ahydroxyl equivalent weight of from 800 to 2000 and a total oxyethylenecontent of from 5 to 18% by weight. Such polyether polyols aredescribed, for example, in U.S. Pat. No. 9,156,936.

The number average molecular weight of the polyether polyol(s) may be,in various desirable embodiments of the invention, in the range of 250to 6500 Daltons. A plurality of polyether polyols having differentnumber average molecular weights may be utilized. Advantageously, theviscosity of each polyether polyol may be in the range of 400 to 21,000cps at 25° C.

The hydroxyl number of the polyether polyol(s) useful in the presentinvention may vary significantly and may be selected in accordance withthe desired properties of the thermoset obtained by reacting the polyolswith organic polyisocyanate or the like. For example, the polyetherpolyols may have hydroxyl numbers of from 200 to 850 mg KOH/g. Mixturesof polyether polyols with different hydroxyl numbers may be used.

Examples of polyether polyols suitable for use in the present inventioninclude, without limitation (provided that they meet the previouslydiscussed apparent pH requirements of the present invention):

Sucrose/glycerin-initiated polyether polyols having hydroxyl numbers of300 to 600 mg KOH/g and functionalities of 4 to 7.

Mannich-base initiated polyether polyols having hydroxyl numbers of from400 to 500 mg KOH/g and functionalities of 3.1 to 3.8.

Aliphatic amine-initiated polyether polyols having hydroxyl numbers offrom 500 to 850 mg KOH/g and functionalities of from 3 to 4.

Sucrose/diethylene glycol-initiated polyether polyols having hydroxylnumbers of from 390 to 490 mg KOH/g and functionalities of from 4 to4.7.

Sorbitol-initiated polyether polyols having hydroxyl numbers of from 440to 540 mg KOH/g and functionalities of from 4.4 to 5.8.

Sucrose/amine-initiated polyether polyols having hydroxyl numbers offrom 440 to 550 mg KOH/g and functionalities of from 4 to 7.

Aromatic amine-initiated polyether polyols having hydroxyl numbers offrom 275 to 550 mg KOH/g and functionalities of 3.2 to 4.0.Ortho-toluene diamine (TDA) and diphenylmethanediamine (MDA) areexamples of aromatic amines.

Examples of commercially available polyether polyols include, but arenot limited to, products sold under the following trade names: JeffolSG-360 (sold by Huntsman), Voranol 490 (sold by Dow Chemical), JeffolR-470X (sold by Huntsman), Jeffol R-425X (sold by Huntsman), JeffolAD-310 (sold by Huntsman), Jeffol AD-500 (sold by Huntsman), JeffolSD-441 (sold by Huntsman), Jeffol S-490 (sold by Huntsman), JeffolSA-499 (sold by Huntsman), Pluracol 1578 (sold by BASF) and Carpol EDAP800 (sold by Carpenter Chemicals).

Prior to use in accordance with the present invention, however, theapparent pH of any commercially-obtained polyether polyol should bechecked using the analytical method described herein to confirm that thepolyether polyol has an apparent pH within the desired range. Performingsuch a check on each batch or lot of polyether polyol is advisable, assome variability in apparent pH may be observed from batch-to-batch orlot-to-lot or as a particular batch or lot of polyether polyol ages. Ifthe apparent pH is found to be outside the desired range, it may beadjusted by combining the polyether polyol with an amount of one or morepH adjusting agents (e.g., acids, bases) which is effective to bring theapparent pH within such desired range, as described elsewhere herein.

Polyester polyols are characterized by having polyester-containingchains and hydroxyl end groups. They are typically produced bypolycondensation of a polyacid (e.g., a diacid) with excess polyalcohol(e.g., diol). The polycondensation may be carried out in the presence ofa catalyst, such as a metal-containing catalyst. To produce polyesterpolyols with branched structures and/or functionalities greater than 2,some amount of polyacid containing more than two acid groups permolecule and/or polyalcohol containing more than two hydroxyl groups permolecule may be employed. While any type of polyester polyol may beutilized in the present invention, the use of aromatic polyester polyolsmay be especially advantageous. Aromatic polyester polyols may beprepared, for example, by utilizing aromatic polyacids as reactants(e.g., phthalic acids). In certain embodiments of the invention, one ormore aromatic polyester polyols are employed having hydroxyl numbers of200 to 450 mg KOH/g and functionalities of 2 to 3. In addition to havingapparent pH values in accordance with the previously discussedrequirement, it will generally be advantageous to select polyesterpolyols having relatively low levels of certain Lewis acid catalysts(e.g., Sb, Ti and Mn-containing catalysts), which are sometimes employedin the manufacture of such polyols but which tend to decrease thestability of the pre-mix. In particular, the polyester polyol(s)employed should desirably contain less than 60 ppm Sb, more preferablyless than 40 ppm Sb and most preferably less than 20 ppm Sb, less than150 ppm Ti, more preferably less than 120 ppm Ti and most preferablyless than 75 ppm Ti, and less than 6000 ppm Mn, more preferably lessthan 4000 ppm Mn and most preferably less than 2000 ppm Mn.

Examples of commercially available polyester polyols include, but arenot limited to, products sold under the following trade names: Terate3510 (sold by Invista), Terate HT 5100 (sold by Invista), Terate 2031(sold by Invista), Terol XO 12009 (sold by Huntsman), Terol 305 (sold byHuntsman), Stepanpol PS 2520 (sold by the Stepan Company), Stepanpol PS3021 (sold by the Stepan Company), Stepanpol PS 3422 (sold by the StepanCompany), Stepanpol PS 3524 (sold by the Stepan Company), and StepanpolPS 2352 (sold by the Stepan Company).

Prior to use in accordance with the present invention, however, theapparent pH of any commercially-obtained polyester polyol should bechecked using the analytical method described herein to confirm that thepolyester polyol has an apparent pH within the desired range. Performingsuch a check on each batch or lot of polyester polyol is advisable, assome variability in apparent pH may be observed from batch-to-batch orlot-to-lot or as a particular batch or lot of polyester polyol ages. Ifthe apparent pH is found to be outside the desired range, it may beadjusted by combining the polyester polyol with an amount of one or morepH adjusting agents (e.g., acids, bases) which is effective to bring theapparent pH within such desired range, as described elsewhere herein.

Polyether/ester polyols are polyols that contain both oxyalkylene andester-containing repeating units. Exemplary suitable polyether/esterpolyols include aromatic polyether/ester polyols having hydroxyl numbersof from 275 to 575 mg KOH/g and functionalities of from 2.8 to 3.5.

In preparing rigid foam, it is preferred that the amount of polyesterpolyol is in the range of 0 to 100 parts per 100 parts of total polyols(pphp) and the amount of polyether polyol is in the range of 100 to 0pphp; it is more preferable that the amount of polyester polyol is therange of 10 to 90 pphp and the amount of polyether polyol is in therange of 90 to 10 pphp; Even more preferably, the amount of polyesterpolyol is in the range of 20 to 80 pphp and the amount of polyetherpolyol is in the range of 80 to 20 pphp. A single polyester polyol or ablend of two or more different polyester polyols can be utilized, aspreviously described. Likewise, a single polyether polyol or a blend oftwo or more different polyether polyols may be employed. The polyolcomponent may be a combination of one, two or more polyester polyols andone, two or more polyether polyols.

In embodiments of the invention in which the pre-mix is comprised of twoor more different polyols, the impact of the apparent pH of anindividual polyol on the gel time and stability of the pre-mix may,generally speaking, be affected by the apparent pH value as well as therelative amount of that polyol in the pre-mix. For example, when theapparent pH of a polyol is around 10 and the apparent pH of the otherpolyol(s) present in a pre-mix is about neutral (ca. 7), the gel timeand stability characteristics of the pre-mix will typically beincreasingly affected in an adverse way as the proportion of the highapparent pH polyol is increased relative to the amount of the otherpolyol(s).

To further illustrate the foregoing, the following table providespreferred and more preferred maximum amounts of polyether polyol orpolyether/ester polyol having a given apparent pH value that may beblended with a polyester polyol (apparent pH=ca. 4-5) to provide apolyol pre-mix containing halogenated hydroolefin blowing agent havingacceptable storage stability.

Apparent pH of Preferred Amount of More Preferred Amount of Polyether orPolyether or Polyether/ester Polyether or Polyether/ester Polyether/Polyol, pbw per 100 pbw Polyol, pbw per 100 pbw ester Polyol TotalPolyol in Pre-Mix Total Polyol in Pre-Mix 7 to 8 Up to 100 Not more than70 Greater than Not more than 80 Not more than 40 8 to 9 Greater thanNot more than 60 Not more than 30 9 to 10 Greater than Not more than 45Not more than 25 10 to 11.4

If the apparent pH of a polyol is measured and found to be outside ofthe range which has been discovered to be advantageous for purposes ofmaintaining the stability of a pre-mix in accordance with the presentinvention, the apparent pH of that polyol may be adjusted by theaddition of an amount of an acid or base effective to bring the apparentpH within the desired range. In particular, if the apparent pH of apolyol is found to be too basic (e.g., in excess of a value of 11.4 or11 or 10 or 9) such that the storage stability of the resulting pre-mixis adversely affected to a significant degree, sufficient acid may becombined with the polyol to provide a polyol having a target pH value. AH⁺ containing compound such as an organic acid, inorganic acid, orcombination of organic acid and inorganic acid may be utilized to reducethe apparent pH of a polyol to desired level. Organic acids such as a C1to C15 carboxylic acid or ester containing at least one carboxylfunctional group (—COOH) are especially suitable for such purpose, inparticular aliphatic organic acids such as octanoic acid, malonic acidand carboxylic esters such as methyl hydrogen malonate and ethylhydrogen malonate. Different organic acids and/or different inorganicacids may be used together in combination, if so desired.

In other embodiments of the invention, the process conditions employedin manufacturing the polyol are selected or controlled so as to directlyprovide a polyol having the desired apparent pH value or having anapparent pH falling within a desired or preferred range. For example,the type of catalyst utilized in synthesizing a polyol may impact theapparent pH of the polyol. The use of a highly acidic catalyst or highlybasic catalyst (e.g., KOH, CsOH) may, for instance, cause the apparentpH of the resulting polyol to be outside the apparent pH range deemeddesirable in order to impart acceptable storage stability to a pre-mixcontaining such polyol. Such a polyol may be further processed to removesuch a catalyst, reduce the content of such a catalyst and/or at leastpartially neutralize such catalyst, thereby adjusting the apparent pH toa value conducive to achieving satisfactory pre-mix stability.Alternatively, a catalyst which is neither highly basic or highly acidicmay be used to prepare the polyol; examples of such a catalyst mayinclude double metal cyanide catalysts, which optionally comprise atleast one ionic surface or interface active compound selecting from thegroup consisting of Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sn(II),Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(IV), Sr(II), W(IV),W(VI), Cu(II) salts.

The pre-mixes of the present invention are capable of forming foamshaving a generally cellular structure, in particular after beingcombined with components (such as organic polyisocyanates) reactive withthe hydroxyl groups of the polyols to thereby form a thermoset. Examplesof thermosetting compositions which may be prepared using the pre-mixesof the present invention include polyurethane and polyisocyanurate foamcompositions, and also phenolic foam compositions, preferablylow-density foams, flexible or rigid.

The invention also relates to foam, and preferably closed cell foam,prepared from a pre-mix in accordance with the description providedherein. The closed cell content that is measured according to ASTM D2856, or ISO 4590, or a method equivalent to the two methods mentioned,is typically greater than 80%, preferably greater than 90%. The thermalconductivity of the foam, which is characterized as R value per inch, istypically greater than 5, preferably greater than 5.5. In some cases offoam application, fire performance is a key safety factor. Fireperformance is characterized by flame spread and smoke developed.Typically, the less flame spread or smoke developed, the better fireperformance of the foam. Flame spread of 200 or less is typicallyrequired, flame spread of 75 or less is preferred, and flame spread of25 or less is even more preferred. A smoke developed value of less than450 is always preferred.

The invention also relates to foam prepared from a pre-mix in accordancewith the description provided herein. Cell gas analysis of the foamshowed that lower levels of degraded products were present in the cellafter the foam was made, as compared to the levels of such degradedproducts present in foams prepared from halogenated hydroolefin blowingagent-containing premixes not in accordance with the present invention.As used herein, “degraded products” refers to the organic compoundspresent within the cells of the foam other than the blowing agent(s) andimpurities coming with the blowing(s) constituents of the blowingagent(s) which were used to prepare the foam. Accordingly, “degradedproducts” are the volatile by-products generated. The levels of degradedproducts such as silanes, e.g., dimethyldifluorosilane, andtrimethylfluorosilane; siloxanes, e.g., hexamethyldisiloxane, arepreferably no more than 20,000 ppm, more preferably no more than 10,000ppm, and even more preferably no more than 5,000 ppm, and even morepreferably no more than 2,000 ppm; and even more preferably no more than1,000 ppm; even more preferably no more than 500 ppm; even morepreferably no more than 250 ppm; even more preferably no more than 130ppm, most preferably no more than 65 ppm. Such concentrations are basedon the total amount of organic compounds measured in the cell gas of afoam (i.e., X parts by weight total degraded products per million partsby weight total organic compounds). The cell gas analysis was performedon a foam according to the procedures described hereafter.

A gas chromatography (GC) method is used to determine the weight percentratio of all organic components that can be detected using FlameIonization Detector (FID) in foam samples using a capillary gaschromatography apparatus, which was calibrated according to theprocedure known to people skillful in art. The following table describesthe method used:

GC: Agilent 6890 Column Type: Restek RTX-1301 Column Length: 105 metersColumn ID: 0.25 mm Film Thickness: 1 μm Temperature program InitialTemp: 30° C. Initial Time: 15 min Rate A: 10° C./min Temperature A: 100°C. Time A: 1.0 min Rate B: 30° C./min Temperature B: 250° C. Time B:15.0 min Total Time: 43 min Type: Helium Head Pressure: 35 psi (constantpressure) Column Flow: 1.4 mL/min Column Velocity: 20 cm/sec InjectionPort Type: Split/Splitless Temperature: 200° C. Split: 25:1 InjectionVolume: 0.5 cc Detector Type: FID Temperature: 250° C.The foam sample is cored using a #5 cork bore, and then pushed out ofthe bore with a glass stirring-rod into a syringe. Use a length of foamto fill approximately 0.5 cc of a 10 cc gas tight syringe. Quicklydepress foam while the syringe is in the GC injection port then startGC.

In certain embodiments of the invention, the B-side polyol pre-mix caninclude (in addition to the previously described blowing agent(s) andpolyol(s)) silicone or non-silicone based surfactants, amine ornon-amine based catalysts, flame retardants/suppressors, acidscavengers, radical scavengers, fillers, and other necessary ordesirable stabilizers/inhibitors as well as other additives conventionalin the thermoset foam art.

Exemplary catalysts include, but are not limited to:N,N-dimethylethanolamine (DMEA), N,N-dimethylcyclohexylamine (DMCHA),bis(N,N-dimethylaminoethyl)ether (BDMAFE),N,N,N′,N′,N″-pentamethyldiethylenetriamine (PDMAFE),1,4-diazadicyclo[2,2,2]octane (DABCO), 2-(2-dimethylaminoethoxy)-ethanol(DMAFE), 2-((2-dimethylaminoethoxy)-ethyl methyl-amino)ethanol,1-(bis(3-dimethylamino)-propyl)amino-2-propanol,N,N′,N″-tris(3-dimethylamino-propyl)hexahydrotriazine,dimorpholinodiethylether (DMDEE), N.N-dimethylbenzylamine,N,N,N′,N″,N″-pentaamethyldipropylenetriamine, N,N′-diethylpiperazine. Inparticular, sterically hindered primary, secondary or tertiary aminesare useful, for example, dicyclohexylmethylamine, ethyldiisopropylamine,dimethylcyclohexylamine, dimethylisopropylamine,methylisopropylbenzylamine, methylcyclopentylbenzylamine,isopropyl-sec-butyl-trifluoroethylamine, diethyl-α-phenyethyl)amine,tri-n-propylamine, dicyclohexylamine, t-butylisopropylamine,di-t-butylamine, cyclohexyl-t-butylamine, de-sec-butylamine,dicyclopentylamine, di-α-trifluoromethylethyl)amine,di-(α-phenylethyl)amine, triphenylmethylamine, and1,1,-diethyl-n-propylamine. Other sterically hindered amines includemorpholines, imidazoles, ether containing compounds such asdimorpholinodiethylether, N-ethylmorpholine, N-methylmorpholine,bis(dimethylaminoethyl)ether, imidazole, n-methylimidazole,1,2-dimethylimidazole, dimorpholinodimethylether,N,N,N′,N′,N″,N″-pentamethyldiethylenetriamine,N,N,N′,N′,N″,N″-pentaethyldiethylenetriamine,N,N,N′,N′,N″,N″-pentamethyldipropylenetriamine,bis(diethylaminoethyl)ether, bis(dimethylaminopropyl)ether, guanidinesincluding pentamethyl guanidine and cyclic guanidines, guanidinederivatives/salts including cyanoguanidine, guanidine hydrochloridesalt, guanidine phosphate salts, guanidine sulfate salts,1-acetylguanidine, nitroguanidine, 1-(o-tolyl)biguanidine, and mixturesthereof, as well as tetraalkyl guanidines that have a formula as in thefollowing:

where R1, R2, R3, and R4 are independently C1-C10 alkyl groups;exemplary tetraalkyl guanidines include tetramethyl guanidine, PolyCat201, 204 (Air Products and Chemicals) and the like; and combinationsthereof.

Exemplary non-amine catalysts include organometallic compoundscontaining bismuth, lead, tin, cadmium, cobalt, iron, thorium, aluminum,mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, zirconium,magnesium, calcium, sodium, potassium, lithium or combination thereofsuch as stannous octoate, dibutyltin dilaurate (DGTDL), dibutyltinmercaptide, phenylmercuric propionate, lead octoate, potassiumacetate/octoate, magnesium acetate, titanyl oxalate, potassium titanyloxalate, quaternary ammonium formates, ferric acetylacetonate andcombination thereof.

The use level of catalyst is typically in an amount of from about 0.1ppm to about 6.00 wt % of the polyol pre-mix, for example from about 0.5ppm to 5 wt % or from about 1 ppm to 4 wt %.

Exemplary surfactants include, but are not limited to, polysiloxanepolyoxyalkylene block co-polymers such as B8404, B8407, B8409, B8462 andB8465 available from Goldschmidt; DC-193, DC-197, DC-5582, and DC-5598available from Air Products; and L-5130, L5180, L-5340, L-5440, L-6100,L-6900, L-6980, and L6988 available from Momentive. Exemplarynon-silicone surfactants include salts of sulfonic acid, alkali metalsalts of fatty acid, ammonium salts of fatty acid, oleic acid, stearicacid, dodecylbenzenedisulfonic acid, dinaphthylmethanedisulfonic acid,ricinoleic acid, an oxyethylated alkylphenol, an oxyethylated fattyalcohol, a paraffin oil, a castor oil ester, a ricinoleic acid ester,Turkey red oil, groundnut oil, a paraffin fatty alcohol, or combinationthereof. Typically, use levels of surfactants are from about 0.1 toabout 6 wt % of the polyol pre-mix, for example from about 0.2 to about4.5 wt % or from about 0.4 to about 3 wt %.

Exemplary flame retardants include trichloropropyl phosphate (TCPP),triethyl phosphate (TEP), diethyl ethyl phosphate (DEEP), diethylbis(2-hydroxyethyl)amino methyl phosphonate, brominated anhydride basedester, dibromoneopentyl glycol, brominated polyether polyol, melamine,ammonium polyphosphate, aluminum trihydrate (ATH),tris(1,3-dichloroisopropyl)phosphate, tri)-2-chloroethyl)phosphate,tri(2-chloroisopropyl)phosphate, chloroalkyl phosphate/oligomericphosphonate, oligomeric chloroalkyl phosphate, brominated flameretardant based on pentabromo diphenyl ether, dimethyl methylphosphonate, diethyl N,N bis(2-hydroxyethyl)amino methyl phosphonate,oligomeric phosphonate, and derivatives thereof.

In certain embodiments, acid scavengers, radical scavengers, and/orother types of stabilizers/inhibitors are included in the pre-mix.Exemplary stabilizer/inhibitors include epoxides such as 1,2-epoxybutane, glycidyl methyl ether and dl-limonene oxide; cyclic-terpenessuch as dl-limonene, 1-limonene and d-limonene; nitromethane;diethylhydroxyl amine; alpha methylstyrene; isoprene; p-methoxyphenol;m-methoxyphenol; hydrazines; 2,6-di-t-butyl phenol; hydroquinone;organic acids such as carboxylic acid, dicarboxylic acid, phosphonicacid, sulfonic acid, sulfamic acid, hydroxamic acid, formic acid, aceticacid, propionic acid, butyric acid, caproic acid, isocaprotic acid,2-ethylhexanoic acid, caprylic acid, cyanoacetic acid, pyruvic acid,benzoic acid, oxalic acid, malonic acid, succinic acid, adipic acid,azelaic acid, trifluoroacetic acid, methanesulfonic acid, orbenzenesulfonic acid; esters, including esters of the aforementionedacids, such as methyl formate, ethyl formate, methyl acetate, isopropylformate, isobutyl formate, isoamyl formate, methyl benzoate, benzylformate or ethyl acetate; and combinations thereof. Other additives suchas adhesion promoters, anti-static agents, antioxidants, fillers,hydrolysis agents, lubricants, anti-microbial agents, pigments,viscosity modifiers, UV resistance agents may also be included in thepre-mix. Examples of these additives include: sterically hinderedphenols; diphenylamines; benzofuranone derivatives; butylatedhydroxytoluene (BHT); calcium carbonate; barium sulphate; glass fibers;carbon fibers; micro-spheres; silicas; melamine; carbon black; waxes andsoaps; organometallic derivatives of antimony, copper, and arsenic;titanium dioxide; chromium oxide; iron oxide; glycol ethers; dimethylAGS esters; propylene carbonate; and benzophenone and benzotriazolecompounds.

The preparation of polyurethane or polyisocyanurate foams using thecompositions described herein may follow any of the methods well knownin the art can be employed, see Saunders and Frisch, Volumes I and IIPolyurethanes Chemistry and technology, 1962, John Wiley and Sons, NewYork, N.Y. or Gum, Reese, Ulrich, Reaction Polymers, 1992, OxfordUniversity Press, New York, N.Y. or Klempner and Sendijarevic, PolymericFoams and Foam Technology, 2004, Hanser Gardner Publications,Cincinnati, Ohio. In general, polyurethane or polyisocyanurate foams areprepared by combining an isocyanate, the polyol pre-mix composition, andother materials such as optional flame retardants, colorants, or otheradditives. These foams can be rigid, flexible, or semi-rigid, and canhave a closed cell structure, an open cell structure or a mixture ofopen and closed cells.

It is convenient in many applications to provide the components forpolyurethane or polyisocyanurate foams in pre-blended formulations. Mosttypically, the foam formulation is pre-blended into two components. Theisocyanate and optionally other isocyanate compatible raw materialscomprise the first component, commonly referred to as the “A-” sidecomponent. The polyol mixture composition, including polyol, surfactant,catalysts, blowing agents, and optional other ingredients comprise thesecond component, commonly referred to as the “B-” side component. Inany given application, the “B-” side component may not contain all theabove listed components, for example some formulations omit the flameretardant if that characteristic is not a required foam property.Accordingly, polyurethane or polyisocyanurate foams are readily preparedby bringing together the A- and B-side components either by hand mix forsmall preparations and, preferably, machine mix techniques to formblocks, slabs, laminates, pour-in-place panels and other items, sprayapplied foams, froths, and the like. Optionally, other ingredients suchas fire retardants, colorants, auxiliary blowing agents, water, and evenother polyols can be added as a stream to the mix head or reaction site.Most conveniently, however, they are all incorporated into one B-sidecomponent as described above. Optionally, one or morenon-water-containing B-side components can be added into the A-side. Insome circumstances, A and B can be formulated and mixed into onecomponent in which water is removed. This is typical, for example, for aspray-foam canister containing a one-component foam mixture for easyapplication.

A foamable composition suitable for forming a polyurethane orpolyisocyanurate foam may be formed by reacting an organicpolyisocyanate and the polyol pre-mix composition described above. Anyorganic polyisocyanate can be employed in polyurethane orpolyisocyanurate foam synthesis inclusive of aliphatic and aromaticpolyisocyanates. Suitable organic polyisocyanates include aliphatic,cycloaliphatic, araliphatic, aromatic, and heterocyclic isocyanateswhich are well known in the field of polyurethane chemistry.

Representative organic polyisocyanates correspond to the formula:

R(NCO)_(z)

wherein R is a polyvalent organic radical which is either aliphatic,aralkyl, aromatic or mixtures thereof, and z is an integer whichcorresponds to the valence of R and is at least two. Representativeexamples of the organic polyisocyanates contemplated herein include,without limitation, the aromatic diisocyanates such as 2,4-toluenediisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluenediisocyanate, crude toluene diisocyanate, methylene diphenyldiisocyanate (MDI), which can exist as different isomers such as2,2′-MDI, 2,4′-MDI, and 4,4′-MDI, with the 4,4′ isomer being most widelyused; crude methylene diphenyl diisocyanate and the like; the aromatictriisocyanates such as 4,4′,4″-triphenylmethane triisocyanate,2,4,6-toluene triisocyanates; the aromatic tetraisocyanates such as4,4′-dimethyldiphenylmethane-2,2′,5,5′-tetraisocyanate, and the like;arylalkyl polyisocyanates such as xylylene diisocyanate; aliphaticpolyisocyanates such as hexamethylene-1,6-diisocyanate, lysinediisocyanate methylester and the like; and mixtures thereof. Otherorganic polyisocyanates include polymethylene polyphenylisocyanate,hydrogenated methylene diphenylisocyanate, m-phenylene diisocyanate,naphthylene-1,5-diisocyanate, 1-methoxyphenylene-2,4-diisocyanate,4,4′-biphenylene diisocyanate, 3,3′-dimethoxy-4,4′-biphenyldiisocyanate, 3,3′-dimethyl-4,4′-biphenyl diisocyanate, and3,3′-dimethyldiphenylmethane-4,4′-diisocyanate; Typical aliphaticpolyisocyanates are alkylene diisocyanates such as trimethylenediisocyanate, tetramethylene diisocyanate, and hexamethylenediisocyanate, isophorene diisocyanate, 4,4′-methylenebis(cyclohexylisocyanate), and the like; typical aromatic polyisocyanates include m-,and p-phenylene disocyanate, polymethylene polyphenyl isocyanate, 2,4-and 2,6-toluenediisocyanate, dianisidine diisocyanate, bitolyleneisocyanate, naphthylene 1,4-diisocyanate,bis(4-isocyanatophenyl)methene, bis(2-methyl-4-isocyanatophenyl)methane,and the like. In one particular embodiment of the invention,polymethylene polyphenyl isocyanates are employed, particularly themixtures containing from about 30 to about 85 percent by weight ofmethylenebis(phenyl isocyanate) with the remainder of the mixturecomprising the polymethylene polyphenyl polyisocyanates of functionalityhigher than 2. These polyisocyanates are prepared by conventionalmethods known in the art. In the present invention, the organicpolyisocyanate and the polyol may be employed in amounts which willyield an NCO/OH stoichiometric ratio in a range of from about 0.9 toabout 5.0. In the present invention, the NCO/OH equivalent ratio may beabout 1.00 or more and about 3.50 or less, e.g., from about 1.05 toabout 3.00. Especially suitable organic polyisocyanates includepolymethylene polyphenyl isocyanate, methylenebis(phenyl isocyanate),toluene diisocyanates, or combinations thereof.

In the preparation of polyisocyanurate foams, trimerization catalystsare used for the purpose of converting the blends in conjunction withexcess A component to polyisocyanurate-polyurethane foams. Thetrimerization catalysts employed can be any catalyst known to oneskilled in the art, including, but not limited to, glycine salts,tertiary amine trimerization catalysts, quaternary ammoniumcarboxylates, and alkali metal carboxylic acid salts and mixtures of thevarious types of catalysts. Preferred species within the classes arepotassium acetate, potassium octoate, and sodiumN-(2-hydroxy-5-nonylphenol)methyl-N-methylglycinate.

The polyurethane or polyisocyanurate foams produced using the pre-mixesof the present invention in combination with one or more organicpolyisocyanates can vary in density from about 0.5 pounds per cubic footto about 60 pounds per cubic foot, preferably from about 1.0 to 20.0pounds per cubic foot, and most preferably from about 1.3 to 6.0 poundsper cubic foot. The density obtained is a function of how much of thehalogenated olefin blowing agent or blowing agent mixture plus theamount of auxiliary blowing agent, such as water or other co-blowingagents, if any, is present in the A and/or B components, oralternatively added at the time the foam is prepared. These foams can berigid, flexible, or semi-rigid foams, and can have a closed cellstructure, an open cell structure or a mixture of open and closed cells.These foams are used in a variety of well-known applications, includingbut not limited to thermal insulation, cushioning, flotation, packaging,adhesives, void filling, crafts and decorative, and shock absorption.

Aspects of the invention include:

1. A polyol pre-mix comprising:

-   -   a) at least one blowing agent, including at least one        halogenated hydroolefin blowing agent; and    -   b) a polyol component comprised of at least one polyol;    -   wherein each polyol of the polyol component has an apparent pH        of at least 3 but no greater than 11.4.        2. The polyol pre-mix of aspect 1, wherein each polyol of the        polyol component has an apparent pH of at least 4 but no greater        than 11.        3. The polyol pre-mix of aspect 1, wherein each polyol of the        polyol component has an apparent pH of at least 4 but no greater        than 10.        4. The polyol pre-mix of aspect 1, wherein each polyol of the        polyol component has an apparent pH of at least 4 but no greater        than 9.        5. The polyol pre-mix of any one of aspects 1-4, wherein the        polyol component is comprised of one more polyols selected from        the group consisting of polyether polyols, polyester polyols,        polyether/ester polyols and combinations thereof.        6. The polyol pre-mix of any one of aspects 1-5, wherein the        polyol component is comprised of one or more polyols having        functionalities of from 2 to 7.        7. The polyol pre-mix of any one of aspects 1-6, wherein the        polyol component is comprised of at least one polyether polyol        and at least one polyester polyol.        8. The polyol pre-mix of any one of aspects 1-6, wherein the        polyol component contains 0 to 100 parts by weight polyester        polyol per 100 parts by weight total polyol component and 100 to        0 parts by weight polyether polyol per 100 parts by weight total        polyol component.        9. The polyol pre-mix of any one of aspects 1-7, wherein the        polyol component contains 10 to 90 parts by weight polyester        polyol per 100 parts by weight total polyol component and 90 to        10 parts by weight polyether polyol per 100 parts by weight        total polyol component.        10. The polyol pre-mix of any one of aspects 1-7, wherein the        polyol component contains 20 to 80 parts by weight polyester        polyol per 100 parts by weight total polyol component and 80 to        20 parts by weight polyether polyol per 100 parts by weight        total polyol component.        11. The polyol pre-mix of any one of aspects 1-7, 9 or 10,        wherein the polyol component is comprised of at least one        polyether polyol and at least one aromatic polyester polyol.        12. The polyol pre-mix of any one of aspects 1-11, wherein each        polyol of the polyol component has a viscosity of from 400 to        60,000 cps at 25° C.        13. The polyol pre-mix of any one of aspects 1-12, wherein each        polyol of the polyol component has a number average molecular        weight of from 250 to 6500 Daltons.        14. The polyol pre-mix of any one of aspects 1-13, wherein the        at least one halogenated hydroolefin blowing agent is selected        from the group consisting of hydrofluoroolefins,        hydrochlorofluoroolefins, and combinations thereof.        15. The polyol pre-mix of any one of aspects 1-14, wherein the        at least one halogenated hydroolefin blowing agent includes        HFCO-1233zd.        16. The polyol pre-mix of any one of aspects 1-15, additionally        comprising at least one surfactant.        17. The polyol pre-mix of any one of aspects 1-15, additionally        comprising at least one catalyst.        18. The polyol pre-mix of any one of aspects 1-15, additionally        comprising at least one surfactant and at least one catalyst.        19. A polyurethane or polyisocyanurate foam which is the        reaction product of a polyol pre-mix in accordance with any one        of aspects 1-18 and at least one organic polyisocyanate.        20. A method of making a polyurethane or polyisocyanurate foam,        comprising reacting a polyol pre-mix in accordance with any one        of aspects 1-18 and at least one organic polyisocyanate.        21. The method of aspect 20, wherein the polyol pre-mix is        prepared by blending the at least one blowing agent and the        polyol component and aging the resulting polyol pre-mix for at        least one month at ambient temperature prior to reacting the        polyol pre-mix with the at least one organic polyisocyanate.        22. A method of making a polyol pre-mix having improved shelf        life, comprising selecting a polyol or plurality of polyols,        measuring the apparent pH of each polyol, confirming that the        measured apparent pH of each polyol is within the range of 3 to        11.4, and combining the polyol or plurality of polyols with at        least one blowing agent, including at least one halogenated        hydroolefin blowing agent, to form the polyol pre-mix.        23. The method of aspect 22, comprising an additional step of        adjusting the apparent pH of at least one polyol prior to        combining the polyol or plurality of polyols with the at least        one halogenated hydroolefin blowing agent.        24. The method of aspect 23, wherein the adjusting of the        apparent pH is carried out by combining the polyol with at least        one C1 to C15 carboxylic acid or ester containing at least one        carboxyl functional group (—COOH).

Within this specification embodiments have been described in a way whichenables a clear and concise specification to be written, but it isintended and will be appreciated that embodiments may be variouslycombined or separated without departing from the invention. For example,it will be appreciated that all preferred features described herein areapplicable to all aspects of the invention described herein.

In some embodiments, the invention herein can be construed as excludingany element or process step that does not materially affect the basicand novel characteristics of the composition or process. Additionally,in some embodiments, the invention can be construed as excluding anyelement or process step not specified herein.

Although the invention is illustrated and described herein withreference to specific embodiments, the invention is not intended to belimited to the details shown. Rather, various modifications may be madein the details within the scope and range of equivalents of the claimsand without departing from the invention.

EXAMPLES Example 1 pH Measurement

pH measurement was carried out at ambient temperature using a Metrohm751 GDP Titrino titrator and an Unitrode Pt1000 (Metrohm part number:6.0258.000, which is equivalent to Corning #476022) equipped with thetemperature compensation function. Standard pH buffer solutions of 4, 7,and 10 purchased from Sigma-Aldrich Co. were used. The calibration wasperformed daily using the three standard buffer solutions. The slopeaccording to the manufacturer's instruction should be within 0.95 to1.05; the typical slope obtained is about 0.99 or 1.00. In order tomeasure apparent pH of a polyol, the procedure of IPA-water method thatwas described previously was followed. A master batch of isopropanol(HPLC grade purchased from Fischer Scientific) and deionized watersolution was prepared using 10 volume parts of isopropanol and 6 volumeparts of deionized water. 50 ml of IPA-water solution was dispensed witha 50 ml auto dispenser, and is about 44.4 g. The pH of the 50 mlIPA-water solution was measured first before adding a polyol, and if thepH was not about 7.00, 0.001 N hydrochloric acid or sodium hydroxide wasadded to adjust the pH to about 7.00. With a magnetic stirrer turned onand when the pH was stable around 7.00, the electrode was removed andabout 10 g of a polyol was added into the solution and stirred for about30 minutes; the electrode was replaced in the solution and allowed tostabilize, and the pH read three times to the nearest 0.01 pH unit.After the measurement, the electrode was removed from the solution andcleaned/maintained using a typical cleaning procedure.

The apparent pH values of 9 polyester polyols and 15 polyether polyolswere measured according to the above procedures; the results aresummarized in Table 1.

TABLE 1 Apparent pH of various polyols Viscosity Apparent Polyol OH #Functionality cps@25° C. pH 1 Polyester #1 280-305 2.2-2.4  6000-100004.74 2 Polyester #2 290-310 2.1-2.3 5000-6000 4.90 3 Polyester #3365-385 2.9-3.1 5500-7500 4.78 4 Polyester #4 290-310 2.1-2.3 5000-60004.76 5 Polyester #5 240-260 2.0-2.1 6000-8000 4.64 6 Polyester #6290-310 2.0-2.2 6000-8000 4.52 7 Polyester #7 340-360 2.1-2.3 6500-85004.73 8 Polyester #8 340-360 2.3-2.5 7000-9000 4.41 9 Polyester #9230-250 2.0-2.1 2500-3500 4.71 10 Polyether #1 460-480 3.2-3.4 8000-840010.21 11 Polyether #2 415-435 3.1-3.3 4400-4600 10.55 12 Polyether #3300-320 3.1-3.3 2300-2500 7.36 13 Polyether #4 490-510 3.1-3.317000-19000 7.26 14 Polyether #5 430-450 4.2-4.4 5000-6000 7.34 15Polyether #6 480-500 4.6-4.8  8000-10000 7.30 16 Polyether #7 485-5054.2-4.4 6000-7000 10.05 17 Polyether #8 350-370 4.6-4.8 3000-4000 8.5918 Polyether #9 470-515 4.0-5.0 5000-7100 9.58 19 Polyether #10 375-4154.0-4.2 17000-20000 10.23 20 Polyether #11 740-825 4.0-4.1 15000-1700011.56 21 Polyether #12 610-655 3.0-3.2 450-490 10.68 22 Polyether #13335-375 4.5-4.7  900-1300 6.00 23 Polyether #14 295-455 4.5-4.72050-3010 6.79 24 Polyether #15 295-355 3.0-3.3 4400-4600 7.39 25Polyether #16 445-555 3.0-3.3  850-1050 7.47

Example 2

In the following examples, foams were made by a hand mix method which isknown to people skillful in the art. B-side mixtures were pre-blendedand then charged into containers that are suitable for pressure up to100 psig. Blowing agents were then added into the B-side container andmixed thoroughly. The B-side containers were then placed in an oven thathad its temperature controlled at about 50° C. (122° F.). The A-side(MDI) and B-side (mixture of the polyol, surfactant, catalysts, blowingagent, and additives) were mixed with a hand mixer and dispensed into acontainer to form a free rise foam after storing in a shaker in whichthe temperature was kept at about 15.6° C. (60° F.). The formulationstested (all had an Iso Index of 110) each contained Rubinate M, apolymeric methylene diphenyl diisocyanate (MDI) available from Huntsman.All polyols were commercially available with desired properties.Tegostab® B 8486 is a surfactant available from Evonik-Degussa. PolyCat®204 and Dabco® T-120 are catalysts from Air Products and Chemicals. TCPPis a flame retardant from ICL-IP America Inc. Total blowing agent levelwas 21.6 mls/g. Table 2 summarizes the formulations used for the study.

TABLE 2 Formulation B-Side PPHP wt % B-side Polyether polyol #8 22.7315.00 Polyether polyol #1 22.73 15.00 Polyester polyol #1 54.55 36.00PolyCat ® 204 4.55 3.00 Dabco ® T-120 0.30 0.20 Tegostab ® B 8486 1.521.00 TCPP 25.16 16.60 Added water 2.12 1.40 1233zd 17.88 11.80 Total BSide: 151.54 100.00 ROH Index 110 Isocyanate 165.24 B/A 0.92 TotalBlowing, ml/gm 21.6

Example 3

Reactivity, gel time (seconds) and tack free time (seconds) weremeasured at the initial time and then 7 days and 14 days after aging at50° C. Samples that were aged at 50° C. were weighed after they wereremoved from the oven to confirm that the loss of component in theB-side was negligible. A and B sides were mixed using an air drivenmixer at about 4000 RPM for 5 seconds to ensure the mixing was thoroughand foam quality was consistently good. Each formula was repeated atleast once, and gel and tack free times were the average of duplicates;the standard deviation was typically about 1 second. The reactivity ofthe formula in Table 2 is summarized in Table 3-1.

TABLE 3 Polyol composition and pH of each component Apparent Polyol PPHPpH Polyether polyol #8 22.72 8.59 Polyether polyol #1 22.72 10.21Polyester polyol #1 54.51 4.74

TABLE 3-1 Reactivity (gel and tack free time) of initial, and 7 and 14day aged at 50° C. Reactivity (seconds) Initial 7 days 14 days Gel time17 24 28 Tack free time 21 32 38

Table 3-1 shows that reactivity decreased as the time of agingincreased, as indicated by the longer gel and tack free times. It isdesired that the reactivity, particularly the gel time, change after 7days of aging at 50° C., be less than 7 seconds, which is equivalent toabout 2 to 3 months of stability under ambient condition. It is evenmore desired that the gel time change after 14 days of aging at 50° C.is less than 7 seconds, which is equivalent to 4 to 6 months ofstability under ambient conditions. Typically, industrial foam producersrequire 2 to 6 months of storage stability for fully blended B-side.Obviously, the above formula has a stability of about 2 to 3 months,which is far short of the more desirable 4 to 6 months stability. US2014/0113984 A1, paragraph [0026], shows that a catalyst such asPolyCat® 204, product of Air Products and Chemicals, may have a pH valueof less than 7. However, PolyCat® 204 alone is not sufficient to renderto the preo-mix the stability that is required.

Comparative Example 3A Observed Stability of 1233zd Replacing HFC245fain a Spray Type Formula

TABLE 3A Formula 245fa 1233zd Terate ® 3510 16.80 16.75 Jeffol ® R-470-X7.35 7.32 Jeffol ® SG-360 7.35 7.32 Ethylene glycol 0.73 0.73 PMDETA(PolyCat ®-5) 0.49 0.49 DMCHA (PolyCat ®-8) 0.98 0.98 Dabco ® T-120 0.100.10 Tegostab ® B 8486 0.49 0.49 Saytex ® RB-79 4.90 4.88 TCPP 2.94 2.93Added water 0.98 0.98 245fa 5.88 — 1233zd — 5.74 Total B Side: 48.9948.71 ROH Index 115 116 Isocyanate 51.0 51.3 B/A 0.96 0.95 TotalBlowing, ml/g 22.0 22.0

The stability of the B-side blend was evaluated by comparing thereactivities of fresh and aged blends at 50° C. for two weeks, as shownin Table 3A-1

TABLE 3A-1 Reactivity change after aging Initial 14 days Reactivity(seconds) 245fa 1233zd 245fa 1233zd Cream time 6 7 7 15 Tack free time15 14 19 48 Rise time 23 22 28 64The reactivity change of B-side blend containing 245fa is acceptable,however, the reactivity change of similar blend after replacing 245fawith 1233zd is not acceptable. It is known to people skillful in artthat a 245fa blend is stable, as Table 3A-1 shows. US 2002/0040070 A1,paragraph [0020], states “Any suitable polyol, as would be apparent tothose of skill in the art, may be used in the present invention.” Inother word, the prior art fails to teach that the apparent pH of anindividual polyol has an impact on the stability of a B-side blendcontaining 1233zd.

Example 4 Replacing Polyether Polyol #1 with Polyether Polyols withDifferent Apparent pH

Polyester polyol #1 and polyether polyol #8, and all other components inthe B-side blends were kept constant; only polyether polyol #1 wasreplaced. Table 4 summarizes the gel time change.

TABLE 4 Reactivity change after replacing polyether #1 polyol Polyether#1 Gel Time Replacement Change (s) Formula Polyol Apparent pH 7 days 14days 1 Polyether #1 10.21 6 11 (control) 2 Polyether #11 11.56 10 16 3Polyether #12 10.68 6 12 4 Polyether #10 10.23 3 9 5 Polyether #9 9.58 613 6 Polyether #2 10.55 6 11 7 Polyether #7 10.05 6 10 8 Polyether #37.36 3 7 9 Polyether #4 7.26 4 7 10 Polyether #5 7.34 5 10 11 Polyether#6 7.30 5 6 12 Polyether #15 7.39 2 4 13 Polyether #16 7.47 2 3 14Polyether #13 6.00 3 5

The experimental data set forth in Table 4 demonstrate that if thepolyol component contains a polyol having an apparent pH greater than11.4 (as is the case for Formula 2, which contained a polyether polyolhaving an apparent pH of 11.56), the gel time increases significantlyafter the premix containing the polyol component and the halogenatedhydroolefin blowing agent has been stored for 7 days or 14 days at 50°C. In contrast, smaller, commercially acceptable increases in gel timewere observed when each polyol of the polyol component had an apparentpH less than 11.4 (as in Formula 1 and 3-14).

Examples 5-9

In these Examples, the effects of the weight ratio of polyester polyolto polyether polyol and the apparent pH of such polyols on the shelfstability of a polyol component were studied.

Example 5

In this Example, a polyether polyol having an apparent pH of 7.30(“Polyol A-5”) was employed as the polyether polyol in a polyolcomponent, either as the sole polyol or in combination with varyingamounts of a polyester polyol (“Polyol B”).

Polyol A-5 was a sorbitol-initiated polyether polyol having a hydroxylnumber of 490 mg KOH/g, an average functionality of 4.7, an averagemolecular weight of 700 Daltons, a hydroxyl equivalent weight of 115Daltons and an apparent pH of 7.30.

Polyol B was an aromatic polyester polyol having a hydroxyl number of295 mg KOH/g, an average functionality of 2.2 and an apparent pH of4.74. The following Table 5-A describes the spray formula employed,while Tables 5-B and 5-C show the foaming results obtained as the weightproportion of polyester polyol to polyether polyol was varied.

TABLE 5-A B-Side PHP wt % B Polyol A-5 X X Polyol B 100-X 66-X PolyCat ®204 4.55 3.00 Dabco ® T-120 0.30 0.20 Tegostab ® B 8486 1.52 1.00 TCPP25.15 16.60 Added water 2.12 1.40 1233zd 17.88 11.80 Total B Side:151.52 100.00 ROH Index 110 Isocyanate 165.21 B/A 0.92 Total Blowing,ml/gm 21.6

TABLE 5-B Reaction time, 5 sec: @60° F. Initial Tack Free Example No.Cream Gel free Rise Foam rise (Formula type) time time time time qualitydensity Example 5-1 9 18 21 34 OK 1.78 (Control) Example 5-2 9 16 19 34OK 1.73 (Polyester Polyol:Polyether Polyol = 100:0) Example 5-3 9 17 2037 OK 1.74 (Polyester Polyol:Polyether Polyol = 85:15) Example 5-4 9 1822 39 OK 1.76 (Polyester Polyol:Polyether Polyol = 70:30) Example 5-5 921 27 45 OK 1.83 (Polyester Polyol:Polyether Polyol = 55:45) Example 5-69 24 33 48 OK 1.86 (Polyester Polyol:Polyether Polyol = 35:65) Example5-7 9 31 41 60 OK 1.88 (Polyester Polyol:Polyether Polyol = 20:80)Example 5-8 11 38 49 68 OK 1.92 (Polyester Polyol:Polyether Polyol =0:100)

TABLE 5-C Example No. % GT Change % GT Change (Formula type) (7 days)(14 days) Example 5-1 (Control) 17 50 Example 5-2 (Polyester 13 38Polyol:Polyether Polyol = 100:0) Example 5-3 17 35 (PolyesterPolyol:Polyether Polyol = 85:15) Example 5-4 16 33 (PolyesterPolyol:Polyether Polyol = 70:30) Example 5-5 14 29 (PolyesterPolyol:Polyether Polyol = 55:45) Example 5-6 13 28 (PolyesterPolyol:Polyether Polyol = 35:65) Example 5-7 13 25 (PolyesterPolyol:Polyether Polyol = 20:80) Example 5-8 21 32 (PolyesterPolyol:Polyether Polyol = 0:100)

Example 6

In this Example, a polyether polyol having an apparent pH of 10.55(“Polyol A-6”) was employed as the polyether polyol in a polyolcomponent, either as the sole polyol or in combination with varyingamounts of a polyester polyol (“Polyol B”).

Polyol A-6 was a sucrose/glycerin-initiated polyester polyol having anapparent pH of 10.55, a hydroxyl number of 490 mg KOH/g, an averagefunctionality of 4.3, and an average molecular weight of 460 Daltons.

Polyol B was an aromatic polyester polyol having a hydroxyl number of295 mg KOH/g, an average functionality of 2.2 and an apparent pH of4.74.

The following Table 6-A describes the spray formula employed, whileTables 6-B and 6-C show the foaming results obtained as the weightproportion of polyester polyol to polyether polyol was varied.

TABLE 6-A B-Side PHP wt % B Polyol A-6 X X Polyol B 100-X 66-X PolyCat ®204 4.55 3.00 Dabco ® T-120 0.30 0.20 Tegostab ® B 8486 1.52 1.00 TCPP25.15 16.60 Added water 2.12 1.40 1233zd 17.88 11.80 Total B Side:151.52 100.00 ROH Index 110 Isocyanate 165.21 B/A 0.92 Total Blowing,ml/gm 21.6

TABLE 6-B Reaction time, 5 sec: @60° F. Initial Tack Free Example No.Cream Gel free Rise Foam rise (Formula type) time time time time qualitydensity Example 6-1 9 18 20 34 OK 1.82 (Control) Example 6-2 8 16 18 31OK 1.74 (Polyester Polyol:Polyether Polyol = 100:0) Example 6-3 9 17 2035 OK 1.75 (Polyester Polyol:Polyether Polyol = 85:15) Example 6-4 9 1822 37 OK 1.78 (Polyester Polyol:Polyether Polyol = 70:30) Example 6-5 923 28 43 OK 1.86 (Polyester Polyol:Polyether Polyol = 55:45) Example 6-610 26 37 49 OK 1.92 (Polyester Polyol:Polyether Polyol = 35:65) Example6-7 10 33 45 61 OK 1.95 (Polyester Polyol:Polyether Polyol = 20:80)Example 6-8 12 48 68 85 OK 1.98 (Polyester Polyol:Polyether Polyol =0:100)

TABLE 6-C Example No. % GT Change % GT Change (Formula type) (7 days)(14 days) Example 6-1 (Control) 27 61 Example 6-2 (Polyester 25 31Polyol:Polyether Polyol = 100:0) Example 6-3 (Polyester 24 47Polyol:Polyether Polyol = 85:15) Example 6-4 (Polyester 33 55Polyol:Polyether Polyol = 70:30) Example 6-5 (Polyester 26 48Polyol:Polyether Polyol = 55:45) Example 6-6 (Polyester 38 Foamcollapsed Polyol:Polyether Polyol = 35:65) Example 6-7 (Polyester 36Foam collapsed Polyol:Poly-ether Polyol = 20:80) Example 6-8 (Polyester22 Foam collapsed Polyol:Polyether Polyol = 0:100)

Example 7

In this Example, a polyether polyol having an apparent pH of 7.26(“Polyol A-7”) was employed as the polyether polyol in a polyolcomponent, either as the sole polyol or in combination with varyingamounts of a polyester polyol (“Polyol B”).

Polyol A-7 was an aromatic amine/DEG-initiated polyether polyol havingan average molecular weight of 465 Daltons, a hydroxyl number of 530 mgKOH/g, an average functionality of 2.9, a hydroxyl equivalent weight of112 Daltons, and an apparent pH of 7.26.

Polyol B was an aromatic polyester polyol having a hydroxyl number of295 mg KOH/g, an average functionality of 2.2 and an apparent pH of4.74.

The following Table 7-A describes the spray formula employed, whileTables 7-B and 7-C show the foaming results obtained as the weightproportion of polyester polyol to polyether polyol was varied.

TABLE 7-A B-Side PHP wt % B Polyol A-7 X X Polyol B 100-X 66-X PolyCat ®204 4.55 3.00 Dabco ® T-120 0.30 0.20 Tegostab ® B 8486 1.52 1.00 TCPP25.15 16.60 Added water 2.12 1.40 1233zd 17.88 11.80 Total B Side:151.52 100.00 ROH Index 110 Isocyanate 165.21 B/A 0.92 Total Blowing,ml/gm 21.6

TABLE 7-B Initial Reaction time, 5 sec: @60° F. Tack Free Example No.Cream Gel free Rise Foam rise (Formula type) time time time time qualitydensity Example 7-1 9 18 21 38 OK 1.77 (Control) Example 7-2 9 17 19 34OK 1.73 (Polyester Polyol:Polyether Polyol = 100:0) Example 7-3 9 16 1832 OK 1.72 (Polyester Polyol:Polyether Polyol = 85:15) Example 7-4 9 1719 34 OK 1.75 (Polyester Polyol:Polyether Polyol = 70:30) Example 7-5 917 20 35 OK 1.80 (Polyester Polyol:Polyether Polyol = 55:45) Example 7-68 17 22 35 OK 1.86 (Polyester Polyol:Polyether Polyol = 35:65) Example7-7 8 19 24 40 OK 1.88 (Polyester Polyol:Polyether Polyol = 20:80)Example 7-8 8 20 27 42 OK 1.95 (Polyester Polyol:Polyether Polyol =0:100)

TABLE 7-C Example No. % GT Change % GT Change (Formula type) (7 days)(14 days) Example 7-1 (Control) 28 50 Example 7-2 (Polyester 18 29Polyol:Polyether Polyol = 100:0) Example 7-3 (Polyester 13 31Polyol:Polyether Polyol = 85:15) Example 7-4 (Polyester 6 12Polyol:Polyether Polyol = 70:30) Example 7-5 (Polyester 6 12Polyol:Polyether Polyol = 55:45) Example 7-6 (Polyester 18 24Polyol:Polyether Polyol = 35:65) Example 7-7 (Polyester 11 21Polyol:Polyether Polyol = 20:80) Example 7-8 (Polyester 15 20Polyol:Polyether Polyol = 0:100)

Example 8

In this Example, an aromatic polyether/ester polyol (“Polyol A-8”) wasemployed as the polyether polyol in a polyol component, either as thesole polyol or in combination with varying amounts of a polyester polyol(“Polyol B”).

Polyol A-8 is an aromatic polyether/ester polyol having a hydroxylnumber of 395 mg KOH/g and an apparent pH of 7.47.

Polyol B was an aromatic polyester polyol having a hydroxyl number of295 mg KOH/g, an average functionality of 2.2 and an apparent pH of4.74.

The following Table 8-A describes the spray formula employed, whileTables 8-B and 8-C show the foaming results obtained as the weightproportion of polyester polyol to polyether polyol was varied.

TABLE 8-A B-Side PHP wt % B Polyol A-8 X X Polyol B 100-X 66-X PolyCat ®204 4.55 3.00 Dabco ® T-120 0.30 0.20 Tegostab ® B 8486 1.52 1.00 TCPP25.15 16.60 Added water 2.12 1.40 1233zd 17.88 11.80 Total B Side:151.52 100.00 ROH Index 110 Isocyanate 165.21 B/A 0.92 Total Blowing,ml/gm 21.6

TABLE 8-B Initial Reaction time, 5 sec: @60° F. Tack Free Example No.Cream Gel free Rise Foam rise (Formula type) time time time time qualitydensity Example 8-1 9 18 21 38 OK 1.92 (Control) Example 8-2 9 17 19 35OK 1.92 (Polyester Polyol:Polyether Polyol = 100:0) Example 8-3 9 16 1832 OK 1.84 (Polyester Polyol:Polyether Polyol = 85:15) Example 8-4 8 1415 29 OK 1.82 (Polyester Polyol:Polyether Polyol = 70:30) Example 8-5 813 14 28 OK 1.80 (Polyester Polyol:Polyether Polyol = 55:45) Example 8-68 14 15 28 OK 1.91 (Polyester Polyol:Polyether Polyol = 35:65) Example8-7 8 15 16 31 OK 1.68 (Polyester Polyol:Polyether Polyol = 20:80)Example 8-8 8 16 18 33 OK 1.68 (Polyester Polyol:Polyether Polyol =0:100)

TABLE 8-C Example No. % GT Change % GT Change (Formula type) (7 days)(14 days) Example 8-1 (Control) 22 44 Example 8-2 (Polyester 6 29Polyol:Polyether Polyol = 100:0) Example 8-3 (Polyester 6 19Polyol:Polyether Polyol = 85:15) Example 8-4 (Polyester 14 21Polyol:Polyether Polyol = 70:30) Example 8-5 (Polyester 23 23Polyol:Polyether Polyol = 55:45) Example 8-6 (Polyester 0 7Polyol:Polyether Polyol = 35:65) Example 8-7 (Polyester 0 0Polyol:Polyether Polyol = 20:80) Example 8-8 (Polyester 0 0Polyol:Polyether Polyol = 0:100)

Example 9

In this Example, a polyether polyol (“Polyol A-9”) having an apparent pHof 8.59 was employed as the polyether polyol in a polyol component,either as the sole polyol or in combination with varying amounts of apolyester polyol (“Polyol B”).

Polyol A-9 is a sucrose/glycerin-initiated polyether polyol having ahydroxyl number of 360 mg KOH/g and an apparent pH of 8.59.

Polyol B was an aromatic polyester polyol having a hydroxyl number of295 mg KOH/g, an average functionality of 2.2 and an apparent pH of4.74.

The following Table 9-A describes the spray formula employed, whileTables 9-B and 9-C show the foaming results obtained as the weightproportion of polyester polyol to polyether polyol was varied.

TABLE 9-A B-Side PHP wt % B Polyol A-9 X X Polyol B 100-X 66-X PolyCat ®204 4.55 3.00 Dabco ® T-120 0.30 0.20 Tegostab ® B 8486 1.52 1.00 TCPP25.15 16.60 Added water 2.12 1.40 1233zd 17.88 11.80 Total B Side:151.52 100.00 ROH Index 110 Isocyanate 165.21 B/A 0.92 Total Blowing,ml/gm 21.6

TABLE 9-B Initial Reaction time, 5 sec: @60° F. Tack Free Sample IDCream Gel free Rise Foam rise (Formula type) time time time time qualitydensity Example 9-1 9 18 21 36 OK 1.82 (Control) Example 9-2 9 17 20 33OK 1.73 (Polyester Polyol:Polyether Polyol = 100:0) Example 9-3 9 18 2237 OK 1.73 (Polyester Polyol:Polyether Polyol = 85:15) Example 9-4 9 1926 39 OK 1.80 (Polyester Polyol:Polyether Polyol = 70:30) Example 9-5 921 33 45 OK 1.81 (Polyester Polyol:Polyether Polyol = 55:45) Example 9-610 28 42 57 OK 1.82 (Polyester Polyol:Polyether Polyol = 35:65) Example9-7 10 33 49 67 OK 1.83 (Polyester Polyol:Polyether Polyol = 20:80)Example 9-8 11 47 68 85 OK 1.85 (Polyester Polyol:Polyether Polyol =0:100)

TABLE 9-C Sample ID % GT Change % GT Change (Formula type) (7 days) (14days) Example 9-1 (Control) 28 56 Example 9-2 (Polyester 18 35Polyol:Polyether Polyol = 100:0) Example 9-3 (Polyester 22 41Polyol:Polyether Polyol = 85:15) Example 9-4 (Polyester 32 47Polyol:Polyether Polyol = 70:30) Example 9-5 (Polyester 38 43Polyol:Polyether Polyol = 55:45) Example 9-6 (Polyester 21 36Polyol:Polyether Polyol = 35:65) Example 9-7 (Polyester 21 39Polyol:Polyether Polyol = 20:80) Example 9-8 (Polyester Foam collapsedFoam collapsed Polyol:Polyether Polyol = 0:100)

The results observed in Examples 5-9 are summarized in the followingTables 10-A, B and C. The gel times and pre-mix stabilities (change ingel time upon aging) measured for formulations using different blends ofpolyester polyol and polyether polyol were qualitatively scored asfollows:

***=very favorable: gel time on Day 0 very similar to gel time offormulation containing only polyester polyol and gel time did not changesignificantly after 7 and 14 days of aging at 50° C.

***=favorable: gel time on Day 0 similar to gel time of formulationcontaining only polyester polyol and gel time did not changesubstantially after 7 and 14 days of aging at 50° C.

**=acceptable; gel time on Day 0 somewhat longer than gel time offormulation containing only polyester polyol and/or gel time increasedsomewhat after 7 and 14 days of aging at 50° C.

*=not acceptable: gel time on Day 0 substantially longer than gel timeof formulation containing only polyester polyol and/or gel time after 7and 14 days at 50° C. increased substantially.

TABLE 10-A Ex. 6 Ex. 6 Ex. 6 Ex. 9 Ex. 9 Ex. 9 Gel Gel Time Gel Time GelGel Time Gel Time Polyester Polyether Time (s) Change (%) Change (%)Time (s) Change (%) Change (%) Polyol Polyol Day 0 Day 7 Day 14 Day 0Day 7 Day 14 100 0 16 25 31 17 18 35 85 15 17*** 24*** 47*** 18*** 22***41*** 70 30 18** 33** 55** 19*** 32*** 47*** 55 45 23** 26** 48** 21**38** 43** 35 65 26* 38* NA* 28** 21** 36** 20 80 33* 36* NA* 33** 21**39** 0 100 48* 22* NA* 47* NA* NA*

TABLE 10-B Ex. 5 Ex. 5 Ex. 5 Ex. 7 Ex. 7 Ex. 7 Gel Gel Time Gel Time GelGel Time Gel Time Polyester Polyether Time (s) Change (%) Change (%)Time (s) Change (%) Change (%) Polyol Polyol Day 0 Day 7 Day 14 Day 0Day 7 Day 14 100 0 16 13 38 17 18 29 85 15 17*** 17*** 35*** 16*** 13***31*** 70 30 18*** 16*** 33*** 17**** 6**** 12**** 55 45 21** 14** 29**17**** 6**** 12**** 35 65 24** 13** 28** 17**** 18**** 24**** 20 80 31**13** 25** 19*** 11*** 21*** 0 100 38** 21** 32** 20*** 15*** 20***

TABLE 10-C Ex. 8 Ex. 8 Ex. 8 Gel Gel Time Gel Time Time Change ChangePolyester Polyether (s) (%) (%) Polyol Polyol Day 0 Day 7 Day 14 100 017   6   29   85 15 16**** 6**** 19**** 70 30 14**** 14****  21**** 5545 13**** 23****  23**** 35 65 14**** 0****  7**** 20 80 15**** 0**** 0**** 0 100 16**** 0****  0****

1. A polyol pre-mix comprising: a) at least one blowing agent, includingHCFO-1233zd; and b) a polyol component comprised of at least one polyol;wherein each polyol of the polyol component has an apparent pH of atleast 4 but no greater than 10 whereby the polyol pre-mix, after beingstored for six months at 23°, exhibits an increase of less than 40% inat least one of gel time or tack free time when combined with an organicpolyisocyante. 2-3. (canceled)
 4. The polyol pre-mix of claim 1, whereineach polyol of the polyol component has an apparent pH of at least 4 butno greater than
 9. 5. The polyol pre-mix of claim 1, wherein the polyolcomponent is comprised of one more polyols selected from the groupconsisting of polyether polyols, polyester polyols, polyether/esterpolyols and combinations thereof.
 6. The polyol pre-mix of claim 1,wherein the polyol component is comprised of one or more polyols havingfunctionalities of from 2 to
 7. 7. The polyol pre-mix of claim 1,wherein the polyol component is comprised of at least one polyetherpolyol and at least one polyester polyol.
 8. The polyol pre-mix of claim1, wherein the polyol component contains 0 to 100 parts by weightpolyester polyol per 100 parts by weight total polyol component and 100to 0 parts by weight polyether polyol per 100 parts by weight totalpolyol component.
 9. The polyol pre-mix of claim 1, wherein the polyolcomponent contains 10 to 90 parts by weight polyester polyol per 100parts by weight total polyol component and 90 to 10 parts by weightpolyether polyol per 100 parts by weight total polyol component.
 10. Thepolyol pre-mix of claim 1, wherein the polyol component contains 20 to80 parts by weight polyester polyol per 100 parts by weight total polyolcomponent and 80 to 20 parts by weight polyether polyol per 100 parts byweight total polyol component.
 11. The polyol pre-mix of claim 1,wherein the polyol component is comprised of at least one polyetherpolyol and at least one aromatic polyester polyol.
 12. The polyolpre-mix of claim 1, wherein each polyol of the polyol component has aviscosity of from 400 to 60,000 cps at 25° C.
 13. The polyol pre-mix ofclaim 1, wherein each polyol of the polyol component has a numberaverage molecular weight of from 250 to 6500 Daltons. 14-15. (canceled)16. The polyol pre-mix of claim 1, additionally comprising at least onesurfactant.
 17. The polyol pre-mix of claim 1, additionally comprisingat least one catalyst.
 18. The polyol pre-mix of claim 1, additionallycomprising at least one surfactant and at least one catalyst.
 19. Apolyurethane or polyisocyanurate foam which is the reaction product of apolyol pre-mix in accordance with claim 1 and at least one organicpolyisocyanate.
 20. A method of making a polyurethane orpolyisocyanurate foam, comprising reacting a polyol pre-mix inaccordance with claim 1 and at least one organic polyisocyanate.
 21. Themethod of claim 20, wherein the polyol pre-mix is prepared by blendingthe at least one blowing agent and the polyol component and aging theresulting polyol pre-mix for at least one month at ambient temperatureprior to reacting the polyol pre-mix with the at least one organicpolyisocyanate.
 22. A method of making a polyol pre-mix having improvedshelf life, comprising selecting a polyol or plurality of polyols,measuring the apparent pH of each polyol, confirming that the measuredapparent pH of each polyol is within the range of 4 to 10, and combiningthe polyol or plurality of polyols with at least one blowing agent,HCFO-1233zd, to form the polyol pre-mix, whereby the polyol pre-mix,after being stored for six months at 23, exhibits an increase of lessthan 40% in at least one of gel time or tack free time when combinedwith an organic polyisocyante.
 23. The method of claim 22, comprising anadditional step of adjusting the apparent pH of at least one polyolprior to combining the polyol or plurality of polyols with the at leastone blowing agent.
 24. The method of claim 23, wherein the adjusting ofthe apparent pH is carried out by combining the polyol with at least oneC1 to C15 carboxylic acid or ester containing at least one carboxylfunctional group (—COOH).
 25. The polyol pre-mix of claim 1, wherein theat least one blowing agent consists essentially of HFCO-1233zd.
 26. Themethod of claim 22, wherein the at least one blowing agent consistsessentially of HFCO-1233zd.